A brief general route for the synthesis of optically active configurational isomers of the biologically important 3-amino-2,3,6-trideoxyhexoses is being studied. The partially developed sequence exploits the use of 4-(E-1-propenyl)-2-azetidinone, which on methanolysis (MeOH/HCl) followed by benzoylation furnishes methyl 3-benzamido-4(E)-hexenoate in 80% yield. Hydroxylation of the olefinic fragment of the hexenoate with trimethylamine-N-oxide and a catalytic amount of osmium tetroxide gives the lyxo and xylo configurational isomers of 3-benzamide-5-hydroxybutyrolactones (92% yield) which are easily separated. Reducation of the individual lactone isomers affords the corresponding amino sugars. The reaction sequence was employed to successfully synthesize the N-benzoyl derivative of daunosamine, the sugar fragment present in several clinically important anticancer antibiotics. Studies are proposed for: 1) inverting the C-5 hydroxyl group of the lyxo and xylo lactone isomers to prepare lactones with the ribo and arabino configurations which are precursors to the amino sugars ristosamine and acosamine, 2) resolving the amino hexenenoate intermediate in order to prepare the optically active configurational isomers, 3) selectively hydroxylating the amino hexenenoate intermediate for stereospecific preparation of configurational isomers. Acosamine, daunosamine, ristosamine, angolosamine, megosamine and rhodosamine will be synthesized using the fully developed sequences. The broad applicability and general nature of the methodology will be demonstrated by performing preparations of vancosamine and evernitrose.